Method of treating a hydrocarbon feed stock with a solution comprising aryl sulfonic acid



G. H. sH'lPLEY, JR.,` E1' Al.

Oct. 7, 1947. 4 2,428,686

uETHonoF TREATING A HYDRocARBoN FEED sTocK WITH Ar fourni SOLUTION GOMPRISING ARYL SULFONIC ACID Filned'May 12, 1945 Mw BY AT1-o R Nav.

Patented Oct. 7, 1947 :METHOD OF TREATING A HYDROCARBON FEED STOCK WITH A SOLUTION COM- PRISING ARYL SULFONIC ACID George H. Shipley, Jr., Baytown, and Glenn W. Wilson, Jr., Goose Creek, Tex., assignors to Standard Oil Development Company, a corporation of Delaware Application May 12, 1945, Serial No. 593,456

l sulfonic acids to remove sulfur, to improve the color, or to enhance the octane number of the hydrocarbons. It is known to treat hydrocarbons in the vapor phase with a solution of aryl sulfonic acid in an organic solvent; it is also old to treat `hydrocarbons with aqueous solutions of sulfonic acids. In the particular instance when aqueous solutions are employed, the aryl sulfonic acids do not exert a catalytic effect, but are consumed in the operation and are rejectedfrom the process as a sludge formed with the reaction products.

AEmployment of thearyl sulfonic acids in an organic solution is disadvantageous by virtue of the fact that the solution is highly corrosive to ordinary steels and requires special alloys ofsteel or copper-bearing metals for safe handling. It is disadvantageous to use the aqueous solution of the sulfonic acids since this results in consumption of the treating reagent as well as consumption of the hydrocarbon undergoing treatment.

We have now found that the disadvantages of the prior art may be overcome by employing the aryl sulfonic acids as solutions of the anhydrous acid in an organic solvent provided arsenic or a compound or arsenic is present during the reaction. In accordance with the present invention, we realize this benecial effect by addingl a small quantity of arsenic to the aryl sulfonic acids and then employ the mixture in services in which the aryl sulfonic acids have been found benecial. We may add arsenic as the element or as a compound and when the compound is used, we may use sodium meta arsenite, arsenic trioxide, arsenic acid, arsenic pentoxide or any other arsenic compound which will dissolve readily in the catalyst solution.

It will be found desirable to maintain the arsenic in the catalyst within the range of .013 to .0013 gram moles of arsenic per 100 grams of catalyst solution, that is to say, the arsenic in the catalyst will ordinarily be less than 1 percent by weight of the total mixture and usually less than .5 percent by Weight will be required. In somefinstances, as little as 0.1 percent by Weight oriarsenic is effective in reducing the 5 Claims'. (Cl. 260-674) corrosivity of the aryl sulfonic acid in organic solutions to the extent that ordinary steel equipment may be satisfactorily employed.

The type of reaction in which the present invention nds use is in treating hydrocarbons to remove undesirable constituents, for example, removing olenic materials from toluene, condensation and polymerization reactions, desulfurization of hydrocarbons and in many other catalytic reactions. The invention is especially useful in preparing nitration grade toluene in which small amounts of olens can not be tolerated.

TheV sulfonic acid maybe selected from the sulfonic acids including benzene sulfonic acid, toluene sulfonic acid, naphthalene sulfonic and any other of the aryl sulfonic acids which may be available. y

The solvent employed is preferably an aromatic hydrocarbon. Benzene, toluene and the homologues of this series of compoundsare especially useful in this respect. It will be desirable to employ from about 5% to 60% by volume of the aryl sulfonic acid inthe solvent. Usually a 30% to 50% solution will form anvelfective catalyst.

The reactions may be carried out in the vapor or liquid phase. Ordinarily when operating in the liquid phase, pressures will be employed to provide liquid phase conditions for the hydrocarbon. The temperatures at which the present invention is conducted may vary from about to 400 F. depending on the type of hydrocarbon being reacted.` When treating toluene for removal of olens with the toluene in the vapor phase, it will be desirable to employ a temperature of about 240 or 250 F. These conditions are particularly suitable when a solution of toluene sulfonic acid dissolved in toluene containing arsenic or its compounds is the treat-A ing medium. Y K

Y The present invention will be further illustrated by reference to the drawing in which the single iigure represents one embodiment. It will be understood that the following description given in conjunction with the drawing of the treatment of toluene Vfor removal of olensis for purposes of illustration only and is not to be considered as limiting our invention to the specic embodiment.

Referring now to the drawing numeral l I designates a charge line throughwhich toluene is in'- troduced into the system. The toluene is heated and vaporized infheater I ,2 and is brought to a temperature of about 250"- F. The heated and vaporized toluene discharges from heater l2 by way of line i3 into contact zone I4 which, inthis parf cending toluene vapors flowing upwardly there-V 1Q through. Treated hydrocarbons emergeY fromY zone I4 by way of line I8 while the catalyst accumulating in zone I6 is withdrawn by. line I9, cooled in cooler 20, and discharigefifbylineV 2l incr-i v to settling zone 22. In settling, zone 22, the cat- 15 alyst is separated from anyV polymers which may have been formed in contact zone I4 and the sep. arated catalyst is withdrawn from zone 22 byline 23 for recycling by lines 24 and I'I back intocon.;

tact Zone I4. Line I'I is provided with heater 25 20 for adjustment. and. maint-,errante or; the, Proper,

temperature. of. ea lyst "adrawoffierroyiaed or .diecardrof used oatalyat.

' edforirrtroduetion Y Q .ifcatalyetfe'ontaiainafareenio Pehtoxise- 25 ,c .c Y i .v Y

' senic pentoiride dissolved man/aromatic, solventr Arly polymers which. accumulate in the Catalyst Separate therefrom in Zone, 2.2.,ar1d may be Withdrawn. byonening valve 2.8;. in line 2.9,. or prefer: ably/may be. retained in the System. ley-routine ther-nto. .linell controlled; by Valve 3J; along With. so

the treated metterlialv line I@ to iraeonation Zone.` 32.* Y v Fractionation zone 32 is provided with a heat: insmeane 3.3.for adjustment of; tenreratilresand nresauras-1ine3.foryyithdrawallof polymers and 3.5.,

fonic. acid anda minor, por

other .heavy material; and; line; 3.5 for.. Withdrawal. of.- the-.'produot.;

The product, issuing as vapors througlrline 35, is Condensed and. cooled in.. Condenser. 3.6. and has intro edjthereinto.. by Way o f5rline 3.7. anal- 4c kali agent The nurture of; alkalinereaserrt and fdhydr` .bonnasses through an, inf. orf dayton awhereinit, intimately pour,

taotedeloeffore. iowine `through `line 33 into settling.Y

Zoaefth Settling-:aaneen isof; suicientoanacity 45;

ton avide residence time rorteeparation by eravty othe,allialirregreasentandthe treated hydro-1 Carb. 1i-he treated hydrocarbon ifs; with'drau/rrr troni` zone; .40.- by ;1f1ne;54.-!... alkaline., reagentV isdi charged 1in forpdieoard rofz, 11S Contains ayalya 1ra-lire reagente 31 Line. 42; contains` avalve 4.4;;

alkalnereasent; and line 31%; f ogc,introrollretion;v otresh al,-4

Prior Ytothe preeentinverrtionthe ferrous metal; 55

equipment. makineup. contact Zone I4. sett-ling Zone 2,A and connecting 1inesbecamerapidly core. r9ded"b;y.tha action of-.thetoluenasulfonic acid. ThefeorrQSiQn rate.was.sosevere that under. some conditions as much as 2.5 inches of thejnewalper 60 yearwas penetrated. Undersimilar conditions when.arsenicpentozgideisused in the amount of 03% bykweiglfit,V the corrosion rate is reduced to 0.0 0 1 inch perv year penetration of the metal.

` Similar results are obtained withsodium meta 65:y

arsenite andother arsenic-containing materials.l In orde/rv to illustrate the invention further, a steel strp'was immersed in acbvoilingl toluene so- 1u'tioncontaininglofweght per cent anhydrous toluene sulfonic acid.v After 27 hours exposure y70 inithe' boilingv solution, it was observed that'the corrosion of. `the steell strip` as reiiected by the penetrationfratefin inches per year was 2.52.

V Similar Stee1etrirairereimmereedin beiline'teluelle.soluteneeertainins.50 weielatrereent tela-V..

byalirreatziandi reeyeled'by branch; 5o.

ene sulfonic acid containing, in one instance, 0.2 Weight percent arsenic pentoxide and in another instance 0.2 Weight percent sodium meta arsenite. The steel strips were allowed to remain in 5 the boiling solutions for '721 2lion-rs aff-ter which thty' 'Wereirenioved waehedxdried andweighed. In the rst instance where the boiling solution was inhibited with arsenic pentoxide, the corrosion rate was found to be 0.001 inch penetration per year;L whilein the/second instance when s0- pdium, meta arsenite Waspresent, the corrosion rate as evidenced by penetration of the metal was V0.1.0.0rA mehrer year f 1t will thus, be; seen that by the practice of the presentfinventiomit is possibleI to employ ordinary steels in` treating hydrocarbons with organic .solutions ot the. aryl sulfonic acids Which results ina considerable saving in capital expenditure.

The nature and objects of the present invention having been fully described and illustrated What We Wish tolill aiw ildgllflilgldlto "1 'A pretese ier treatiaea hydratante@ reeelv stockwhichcornprises contacting the feed st with a4 solution. of toluffiniahV sulfonic. acidV4 and.:

Oxide? ds'fiolvf'iriafarbmat `3l4mt130a in accord e; witlrelairn 2:2 'fr which Said. Solution am .Hees toluene.. eritema acid Within the range Yot. f i 1 n and arsenic pentoxide *withiriftherangeof; 001.3 119.10913 'aramaoleeaer 10.0 grams. o ffeomti 4s. A'. Process fior; treaties; ah,ydrotarborev feed: Sto Whiercomprises. Contadina the. reed stock;

with "a SOltiQrl committing@ maior portion.v ofKA e aryllsulfonic acid andina y norportion of arsenic: reptaXideS diseelyed; in af1'1..one-1rr1 eI solvent#Y temi?eraturerwithin;t.` .use from; 109- togen()9 5.V -A- process or treating1a.;.hydroearhongieed-. stock which comprises'contacting the ieedtgck; WithY a .SQIUGOH .C Qmllaing. arylzeulfonc; .acid Within'the raaeeort 9150.1/ 11 ener. een and.; areerire rentraide withmheranee.: ofi 010.13a1a1r1, malesrrer -lfsrarns;.orrsoluti n di solved in; an organic :solvent ata temperature-e the rangeofflzoo QQQIEQ v .VZ-.WlllfSONn .R-,j

Theiollowing references are ,ofI-ifecgjfdlinirth lefefithiS-Lrateei t Number..-

Y tirata i;

oavalurre per eentf 

